Water-soluble reactive azo dyes



United States Patent 3,222,354 WATER-SOLUBLE REACTIVE AZO DYES GuenterLange, Ludwigshafen (Rhine), Germany, assignor to Badische Anilin- &Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany N0Drawing. Filed Mar. 15, 1963, Ser. No. 265,332 Claims priority,applicatiog Gil-many, Mar. 17, 1962,

9 Claims. (Cl. 260163) Y-N' N-li-dt an;- 1" n- 1 d in which:

Y denotes a reactive acyl radical which contains up to six carbon atomsand which is unsaturated in cap-position or reacts under the conditionsof dyeing and printing with the hydroxyl groups of fibrous material likesuch a radical,

K denotes the radical of a coupling component, preferably of thenaphthalene or pyrazolone series (the coupling component if desiredcontaining an azo linkage) and n denotes one of the whole numbers 1, 2and 3.

Coupling components having one or more sulphonic acid radicals arepreferred, but azo dyes not having watersolubilizing radicals in thecoupling component are also excellent products.

The new azo dyes may be prepared by coupling diazoniurn compounds withcoupling components in such a way that there is present in the moleculeof the azo compound obtained at least one radical of the generalformula:

HO 3 s I Hm-rn-i X in which one X denotes a hydrogen atom and the otherX denotes an azo bridge, n denotes a whole number, preferably and Ydenotes a hydrogen atom or the acyl radical of an a,,8-unsaturatedcarboxylic acid having at the most six and preferably three to fourcarbon atoms, or an acyl radical which under dyeing conditions may beconverted into an a,}8-unsaturated carboxylic acid radical having thesaid number of carbon atoms, Y, when it denotes hydrogen, then beingreplaced by an acyl radical of the said kind. The hydrogen ion in the HOS- group in the above formula may also be replaced by another inorganicor organic cation, for example by sodium or potassium. Those dyes arepreferred in which the X in para-position tothe YN radical constitutesthe azo bridge. The radical of acrylic acid is particularly suitable asthe radical of an 0a,]3-11I1S3t111'21t8d carboxylic acid. The

3,222,354 Patented Dec. 7, 1965 acrylic acid radical may also containfor example halogen atoms or alkyl and/or carboxylic or carboxylic amidegroups. The acyl radicals of the alkyl (preferably methyl and ethyl)and/or halogen substitution products of acrylic acid, such asa-methyland/or fi-methyland/or dimethylacrylic acid, a-monoand/ orB-monoand/ or dichloroacrylic acid, and also maleic acid and themonochloromaleic and/ or dichloromaleic acids, are therefore alsosuitable. The monochloromaleic acid radical is preferred. Thea,B-linkage may also be acetylenically unsaturated, as for example inpropiolic acid, the radical of which is also particularly suitable.

Examples of acyl radicals which are convertible under dyeing conditionsinto the radical of. an anti-unsaturated carboxylic acid areparticularly the radicals of fl-halopropionic acids or theirsubstitution products and especially the fi-chloropropionyl radical ofwhich it is known that under conditions such as are usual in dyeing orprinting with reactive dyes it is readily converted int-o the (1,5-unsaturated carboxylic acid radical. It may be generally stated,however, that reactive radicals which considerably increase thewater-solubility of the finished dye are not preferred.

The radical C,, H is advantageously hydrogen (n=l), but may also bemethyl (n=2) or ethyl (n=3). Values of n which are higher than this donot offer any particular advantage over the said values within the scopeof the present invention.

Anhydrides or acid halides may be used for the introduction of the acylradicals Y into the diazo components.

In principle, all compounds capable of coupling may be used as couplingcomponents for the new reactive azo dyes, particularly phenols,naphthols, naphtholsulfonic acids, aminonaphthols, aminonaphtholsulfonicacids, acylaminonaphthols whose acyl radical may be reactive, arylaminonaphtholsulfonic acids, S-pyrazolones and their sulfonic acids, and alsohydroxyquinolines and azo compounds capable of coupling. If the couplingcomponents in turn contain diazotizable amino groups or amino groupderivatives convertible into the same, the dyes obtained may be reactedto form disazo dyes. Individual examples of coupling components whichmay be used in the process of this invention are given in the followingexamples. Coupling components which contain a sulfonic acid group arepreferred.

The dyes thus obtained lend themselves admirably to the reactive dyeing,particularly by the so-called padbatch process, of fibers and other highmolecular weight compounds whose molecules have groups which underdyeing conditions can enter into chemical combination with the reactiveradical. Examples of such groups are hydroxyl groups. Accordingly thefollowing are examples of materials suitable for dyeing: cotton, rayonstaple, viscose, Wool, silk, leather, and skins. The new dyes areparticularly suitable for printing. Dyes obtainable according to thisinvention are distinguished by brilliance of shade and very good Wet andlight fastness. In printing and pad-batch processes and in theirsolubility, the dyes according to this invention are superior to theprior art azo dyes derived from diazo components having the generalformula:

SIOaH The prior art azo dyes derived from diazo components having theformula:

are also inferior in solubility, dyeing and printing to the new dyesobtainable according to this invention.

By reactive dyeing we mean dyeing and printing processes whose object isto cause a chemical combination of the reactive dye with fiberscontaining reactive groups or with other substances capable of reaction,under the influence of basic compounds, for example mild alkali, such assodium hydrogen carbonate, or also of strong alkali such as sodiumhydroxide in aqueous phase, at elevated temperature and/or with longstorage of the dyed or printedmaterial.

The invention is further illustrated by the following examples in whichparts are by weight.

EXAMPLE 1 48.4 parts of 1-amino-4-acryloylaminobenZene-3-sulfonic acidis dissolved in 200 parts of water with the addition of 20 parts ofcaustic soda solution (10 moles/1.). 40 parts of a M sodium nitritesolution is added to the neutral solution, 400 parts of ice introducedand diazotization effected by pouring in 50 parts of hydrochloric acidmoles/ 1.). The suspension of the diazonium salt is then allowed to flowinto a coupling solution prepared from 200 parts of water, 50.6 parts ofsodium 1-hydroxynaphthalene-4-sulfonate, 25 parts of caustic sodasolution (10 moles/l.) and parts of sodium carbonate solution (1.25moles/1.). Coupling is soon ended. The deposited dye is filtered offwith suction and washed with about 100 parts of a 10% sodium chloridesolution. The product is dried at about 70 C. and a dark red powder isobtained which dyes cotton, rayon staple and viscose very fast redshades of great tinctorial strength.

EXAMPLE 2 12.1 parts of l-amino-3-acryloylaminobenZene-4-sulfonic acidis dissolved in parts of water with an addition of 5 parts of causticsoda solution. 10 parts of a 5 M sodium nitrite solution and 50 parts ofice are introduced into the neutral solution. 13 parts of hydrochloricacid 10 moles/l.) is then poured in and the whole stirred for aboutanother hour. The hydrochloric acid suspension of the diazonium salt isthen added to a coupling solution prepared from 50 parts of water, 15parts of 1-(2-chloro- 5-sulfo)-phenyl 3-methylpyrazolone-(5), 11 partsof caustic soda solution (10 moles/l.) and 40 parts of sodium carbonatesolution (1.25 moles/1.). The coupling is rapidly ended and then theyellow dye formed is salted out by adding parts of potassium chloride,the whole stirred for about ninety minutes and the dye then filtered offwith suction and dried at 60 C. under subatrnospheric pressure.

The yellow orange dye powder thus obtained dyes wool, silk, leather andparticularly cotton, rayon staple and viscose rayon very fast clearyellow shades.

The dyes specified in the following table may be prepared in the sameway:

Example N0. Diazo component Coupling component Shade on cotton CH NH:

I ZN c1 3 H 0 Yellow.

CN S0 211 ll 0 I I S0 311 NBC 0 OH=C1I2 I r r 4 Scarlet.

NH O O CH=CH2 S 0 3H S 0 3H 5 I OH Scarlet.

H O as 6 II Orange.

3'0 311 7 I Scarlet.

8 II H038 Orange.

OH 111110 0 CH3 9 I Bluish ruby.

10 II HOsS S0311 Ruby.

on NHC 00112-011201 11 I I Bluish ruby.

12 II Ruby.

Example N0. Diazo component Coupling component Shade on cotton 0 H NHC OC H: 13 I Ruby.

14 TI Red.

HOzS SOBH OH NHOOCH=OH2 1% T Ruby.

HOaSK/ 16 II I Red.

NH0 0 CH3 17 T Red.

HOaS-- 18 IT I Scarlet.

OH 10 T Red.

20 II Yellowish HO S red.

H2? $|l-CI-Is 21 l' 0=O\ /N Yellow.

22 II Yellow.

Hz(|J--(fi-CH3 23 I O=C N Yellow.

HsC Cl 24 II Greenish yellow. SOsH HzC-CCH3 25 I O=C N Reddish yellow.

26 II Yellow.

H1C-CCH 27 I I l Greenish 0:0 N yellow.

N Greenish 28 II H yellow.

(|)H 29 I Ochre. 3O II I Ochre.

31 I. @G Brown. 32 II Brown.

24.2 parts of 1-amino-4-acryloylaminobenzcne-3-sulfonic acid isdissolved in 100 parts of water with the addition of parts of causticsoda solution (10 moles/1.). parts of a 5 M sodium nitrite solution and200 parts of ice are added to the neutral solution and then parts ofhydrochloric acid (10 moles/l.) is poured in.

The hydrochloric acid dispersion of the diazonium salt is neutralized bythe slow addition of 10 parts of sodium hydrogen carbonate to a pH whichis just acid to congo red. The resultant suspension is then added to43.9 parts of 1 amino 8 hydroxynaphthalene-B,6-disulfonic acid which haspreviously been dissolved in 200 parts of water by adding just thenecessary amount of sodium carbonate. After stirring for several hours,the intermediate dye has Example No. Diazo component Coupling componentShade on cotton H2? (ll-CH3 33. I. 0=C N Yellow.

34 II Greenish.

yellow.

NH, C| H 35 Red.

NH(fiCH=CHCl O l S0 11 S0311 NH: (RI NHC0OH=OH2 36 Ruby.

NHCOH=CHOI HOaS- SO3H l HOaS NHz HA]? (6-0113 0:0 N 37 Yellow.

NHCOH=OHCl II O1 0 H0 8 NH; OH NH0 0 CH3 88 Red.

NH(fiOH=0H-CH3 HOaS I 0 H038 SOQH EXAMPLE 39 coupled in the range justacid to congo red. The product is salted out with parts of potassiumchloride and filtered oif with suction. The paste thus obtained is thenstirred into 300 parts of water and another diazonium salt suspensionprepared as above from 24.2 parts of l-arnino-4-acryloylaminobenzene-3-sulfonic acid is added. A pH value of 8.5 isset up by adding 130 parts of a 1.25 M sodium carbonate solution, thewhole stirred for several hours, and the product salted out by adding 40parts of sodium chloride, filtered oil with suction and dried at C.under subatmospheric pressure. powder is obtained which dyes cotton veryfast clear navy blue shades. The two coupling processes may also becarried out in a single stage. The disazo dye is outstandingly suitablefor black dyeing when using large amounts of dye.

Example No. 1st Diazo component Coupling component 2nd Diazo componentShade on V cotton NE: NH: (|)H IIIHQ 40 Navy blue.

SO3H HOzS SOaH NHOOCH=OH= I NHCOOH=CH1 SO H A black dye Example N 0. 1stDiazo component Coupling component 2nd Diazo component Shade on cottonNH: NH; (|)H 11111;

Navy

blue. NHOOCH=CH1 H038 SO3H NHCOCH=CH2 l l SOzH S 03H N112 N 2 lYl z 42Navy blue,

SO H H038 SO3H SOaH I l I NHCOCHrOEhCl NHCOCH O1-I01 ITIH IITHZ (I)H NH;

43 Navy blue.

-SO2H H033 SO3H l l NHCOCHrCHzCl S0311 NHCOCH=CH2 lTIH; NE; on NH;

44 Navy blue.

SO:H HOaS \/-SOaH -SO3H l NHCOCH=CH2 NHCOOH=CH2 The dyes shown in thefollowing table may be prepared by the methods described in Examples 1and 2.

Example No. Dlazo component Coupling component Shade on cotton NH: OH

45 Red.

-SO H l l NHCOCH2CH2C1 SOaH III 0 H NBC 0 CH: 46 .2 III Bluish ruby.

H0 8 SO H Hz? CCH 47 III O=C N Yellow.

HaCfi]I-CH| 48 III 0 0 N Yellow.

HOaS

Example No. Diazo component Coupling component Shade on cotton H2CCCH349 II I I] Yellow.

O=C N 50 III Yellow.

Some of the preferred dyes according to this invention 2. Awater-soluble reactive azo dye as claimed in are specifically listedbelow: claim 1 wherein at least one sulfonic acid group is attached toan aromatic nucleus of the coupling component. ple 1 3. A Water-solublereactive azo dye as claimed in claim Hols 011 1 wherein K is ahydroxynaphthalene radical substituted I by at least one sulfonic acidgroup and coupled to the E;C:OHC O-NH \N=N/\ radical of the formula0rn=cHc0NH- I $02K S OaH Example 3 I 4. A water-soluble reactive azo dyeas claimed in claim 1 wherein K is a hydroxynaphthalene radical sub-HOIS stituted by at least one sulfonic acid group and coupled Q I 01 tothe radical of the formula HnC=CHC ONH N=NO 80:11 NHCOCH=CH1 Example 95. The dye having the formula:

OH NHCOCH! Example 33 sOaH CH; 6. The dye having the formula: HOaS I C:CH3 o1 HOBS I HzC=CH-C ONH N=Nc I l C1 \CN 11,0:011-0 ONHN=NC I OH IExample 44 V OH S OaH 1103's H21? IIOH. SOaH n,c=cno ONHN=N-N=N-NH-co0n=om HOQS- SO3H and the corresponding fl-chloropropionyldyes. 7. The dye having the formula:

I claim: 1. A water-soluble reactive azo dye of the formula Boss OHNHCOCH:

nose I I I HIC=CHC ONHN=N E038 SOaH wherein: I 8. The dye having theformula:

Y denotes a reactive acyl radical selected from the group consisting ofacrylyl, methacrylyl, chloracrylyl 11038 F and fl-chlortpropionyl; I 01K denotes a coupling component selected from the HIC=CH C I I groupconsisting of the hydroxynaphthalene and 3- N methyl-porazolone-(S)series; and

I n is an integer of from 1 to 3, inclusive. I 7 e OH 13 14 9. The dyehaving the formula:

11038 Half 111 SIOzH mc=011-c O-NHN=N N=N-NH-C OCH=CH1 HOsS -SOBHFOREIGN PATENTS References Cited by the Examiner g gfl i UNITED STATESPATENTS 1,212j810 10/1959 15 1239 052 7/1960 France. 2,374,158 4/1945Kmght et a1 260-499 2,931,795 4/1960 Heckendorn et a1. 260--198X 848,7429/1960 Great Bumm- 3,007,762 11/1961 Wegmann et a1. 260-463 X CHARLES B.PARKER, Primary Examiner.

1. A WATER-SOLUBLE REACTIVE AZO DYE OF THE FORMULA